US7670407B2 - Method of producing titanium - Google Patents

Method of producing titanium Download PDF

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US7670407B2
US7670407B2 US11/795,890 US79589005A US7670407B2 US 7670407 B2 US7670407 B2 US 7670407B2 US 79589005 A US79589005 A US 79589005A US 7670407 B2 US7670407 B2 US 7670407B2
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Gerard Pretorius
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Peruke Pty Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
    • C22B34/1213—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by wet processes, e.g. using leaching methods or flotation techniques
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
    • C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
    • C22B34/1245—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a halogen ion as active agent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
    • C22B34/1259—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching treatment or purification of titanium containing solutions or liquors or slurries
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12181—Composite powder [e.g., coated, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12681—Ga-, In-, Tl- or Group VA metal-base component

Definitions

  • This invention relates to the production of titanium metal, titanium alloys and titanium compounds.
  • Titanium is usually commercially produced from titanium tetrachloride (TiCl 4 ) by the Hunter or Kroll processes. These processes involve a sodium or a magnesium reduction step. Titanium has also been produced by the reduction of potassium hexafluorotitanate (K 2 TiF 6 ) with sodium, by the electrolytic reduction of titanium dioxide (TiO 2 ) and by the reduction of TiO 2 with magnesium or calcium. Titanium can accordingly be produced from a variety of titanium-containing precursors using a variety of reducing agents.
  • titanium metal The density of titanium metal is about 45% of that of steel, however titanium is as strong as steel and has superior chemical resistance. Titanium is also the ninth most abundant element in the Earth's crust, but despite its abundance and superior properties, the world market for titanium is only 1% of the aluminium market and only 0.1% of the stainless steel market. The reason for this is its price. Only limited markets such as the military, aerospace and medical markets can afford to use titanium. The main reasons why titanium metal is so expensive are because the precursors used in the production of titanium are expensive and because of high losses due to oxidation during the melting, casting and forging of the metal.
  • the present invention provides an efficient and inexpensive process for the production of titanium, its alloys and its compounds.
  • a method of producing titanium metal from a titanium-containing material including the steps of
  • M II In the case of nitrate, M II will be in its highest oxidation state.
  • M II may be selected from Fe 2+ , Mn 2+ , Zn 2+ , Mg 2+ , Cu 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Co 2+ and Ni 2+ .
  • the alkali metal may be selected from lithium, sodium and potassium.
  • M II TiF 6 will be FeTiF 6 and (M I )aXb will be NH 4 Cl.
  • the titanium-containing material may be selected from ilmenite, rutile, anatase, perovskite, brookite, pseudo-brookite, sphene, leucoxene and titaniferous slags.
  • Ilmenite is FeTiO 3 .
  • Rutile, anatase, brookite and leucoxene are all naturally occurring TiO 2 -containing minerals.
  • Titaniferous slag is a TiO 2 -containing material produced largely from the smelting of ilmenite.
  • Sphene is CaTiSiO 5 and perovskite is CaTiO 3 .
  • the ratio Ti:M II will be adapted to be 1:1 or higher so that the molar amount of M II is at least equal to that of the Ti or higher. This can be achieved by either the addition of Ti or by the addition of M II .
  • the M II TiF 6 may thus be FeTiF 6 and the solution of FeTiF 6 may be produced by the digestion of ilmenite with aqueous HF.
  • the ilmenite may be used in excess.
  • the concentration of the HF may be between about 5 and 60%. Preferably, it will be between about 20 and 24%.
  • the method may include the step of adding a reducing agent to the solution produced in the digestion step to reduce at least some of any Fe (III) present in the solution to Fe(II).
  • the reducing agent may be a metal reducing agent.
  • the metal may be selected from Fe, for example in the form of iron filings or steel wool, Al, Zn, Cu, Mn and Mg.
  • the method may include adding the (M I )aXb in the solid state to the solution produced in the digestion step.
  • the method may include the further step of purifying the M II TiF 6 by recrystallisation.
  • the method may include dissolving the (NH 4 ) 2 TiF 6 in water to produce a solution and precipitating Li 2 TiF 6 , Na 2 TiF 6 or K 2 TiF 6 by the addition of a lithium, sodium or potassium salt to the solution.
  • the salt may be selected from alkali metal chlorides and sulphates but, naturally, any other suitable alkali metal salt may be used.
  • the salt will be sodium chloride or sodium sulphate.
  • the method may then include the step of reducing the Li 2 TiF 6 , Na 2 TiF 6 or K 2 TiF 6 to produce titanium.
  • This route is referred to below as Option A.
  • the reduction may be carried out with a reducing agent selected from sodium, magnesium, potassium and calcium.
  • the method may include, prior to the reduction step, the step of mixing the Na 2 TiF 6 with a predetermined quantity of at least one other metal salt so that the titanium produced in the reduction step is in the form of a titanium alloy containing at least one other metal.
  • the other metal salt may, for example be Na 3 AlF 6 or Na 2 VF 7 or a combination thereof so that the titanium alloy produced contains aluminium or vanadium or both.
  • the method may include, for example, adding sufficient Na 3 AlF 6 and Na 2 VF 7 to produce grade 5 titanium (which contains about 6% aluminium and about 4% vanadium).
  • grade 5 titanium which contains about 6% aluminium and about 4% vanadium.
  • Naturally other metal fluoride salts such as AlF 3 , VF 5 , VF 4 or VF 3 could be used and the amount varied so that a variety of alloys can be prepared.
  • the method may include the steps of first forming an aqueous HF solution of the M II salt and then digesting the titanium-containing material in the acidic solution of the M II salt to produce the solution of M II TiF 6 .
  • the method may include the step of reducing the (NH 4 ) 2 TiF 6 , in which the titanium is in the oxidation state IV, to produce a titanium-III product, decomposing the titanium-III product to produce TiF 3 and reducing the TiF 3 to titanium.
  • This route is referred to below as Option B.
  • the (NH 4 ) 2 TiF 6 may be reduced to the Ti(III) product with a reducing agent selected from aluminium, manganese, zinc, iron and magnesium. Instead, the (NH 4 ) 2 TiF 6 may be electrolytically reduced to produce the Ti(III) product.
  • the Ti(III) product for example, may be (NH 4 ) 3 TiF 6 , (NH 4 ) 2 TiF 5 , or NH 4 TiF 4 . All of these compounds decompose between about 400 and 700° C. to produce TiF 3 .
  • the TiF 3 may be reduced to titanium by reduction with a reducing agent selected from sodium, magnesium and aluminium.
  • the invention extends to TiF 3 produced by the pyrolytic decomposition of NH 4 TiF 4 .
  • the invention extends, further, to TiF 3 having an x-ray diffraction pattern as set out in FIG. 6 .
  • the invention extends further to a method of producing titanium metal from a TiO 2 -containing material, the method including the steps of
  • the TiO 2 -containing material may be selected from rutile, anatase, brookite, leucoxene and titaniferous slag. However, any other suitable TiO 2 -containing material may be used.
  • the aqueous hydrofluoric acid solution containing M II may be prepared by dissolving a basic salt of M II in aqueous HF.
  • the basic salt may for example be the oxide, hydroxide or carbonate of M II .
  • M I will be NH 4 + and the method will include
  • a method of forming a metal alloy including the steps of
  • the method may include combining the fluoride salt of the first metal with two or more reducible salts of other metals so that an alloy containing three or more metals is produced.
  • the reducible fluoride salt of the first metal may be a reducible salt of titanium.
  • the reducible salt of the other metal may be a reducible salt of metals selected from vanadium, aluminium, palladium, molybdenum and nickel.
  • the reducible salt of the first metal may, in particular, be M 2 TiF 6 and the reducible salt of the other metal may be selected from M 3 AlF 6 , M 2 VF 7 and combinations thereof in which M is an alkali metal.
  • M may be sodium.
  • the method may include the further step of smelting the mixture to produce the alloy.
  • a salt which is NH 4 TiF 4 .
  • the invention extends to NH 4 TiF 4 having an x-ray diffraction pattern as set out in FIG. 5 .
  • a method of making NH 4 TiF 4 including the step of reducing (NH 4 ) 2 TiF 6 .
  • the reducing agent may be a metal reducing agent. It may, for example, be aluminium, an aluminium amalgamate, mercury coated aluminium eg Al(Hg) or aluminium carbide.
  • the method may include the further step of
  • the method may include heating the reduction product until the AlF 3 on the surface of the titanium metal powder comprises between about 0.005 and 40% of the mass of the material, preferably between about 0.05 and 10% and more preferably between about 0.1 and 5.0%.
  • the residual AlF 3 causes an inert layer which is at least a monolayer thick to be formed on the surface of the titanium powder. This substantially increases the temperature at which spontaneous combustion of the titanium powder takes place in air from about 250° C. to above 600° C.
  • the powder is accordingly safer to use and transport than prior art titanium powders.
  • the invention extends to a deactivated titanium powder having a surface layer of AlF 3 in which the AlF 3 comprises between about 0.05 and 10% of the mass of the material and preferably between about 0.1 and 5% AlF 3 .
  • the invention extends further to a method of making titanium metal powder the method including the steps of
  • a method of preparing a titanium artifact from a titanium metal precursor material which includes the steps of subjecting the titanium metal precursor material to a heating step to produce a titanium metal intermediate material and subjecting the intermediate material to one or more process steps to produce the artifact, there is provided the improvement of conducting the heating step in an atmosphere containing a volatile fluoride salt.
  • the titanium metal intermediate material produced will thus have a protective layer of the fluoride salt.
  • the atmosphere will preferably be an inert atmosphere such as an argon or helium atmosphere.
  • the titanium metal precursor material may be deactivated titanium powder as hereinbefore described.
  • the volatile fluoride salt may be selected from AlF 3 , MgF 2 and NaF. Naturally, any other suitable fluoride salt may be used.
  • the heating step may be by firing or furnace heating using, for example, vacuum furnaces, inert gas furnaces, microwave assisted furnaces, radio frequency assisted furnaces, induction furnaces or zone refining furnaces.
  • the process steps may be standard process steps of the type used in the fabrication of titanium artifacts such as uniaxial pressing, cold isostatic pressing, hot isostatic pressing, cold rolling, hot rolling and the like.
  • the process steps may include the addition of sacrificial binders such as waxes and polymers.
  • the titanium artifact may be a solid material or a porous material. It may be an alloy of titanium and may be selected from rods, bars, wires, sheets and the like.
  • the titanium artefact may contain trace quantities of fluoride.
  • trace quantities is meant quantities which do not affect the bulk properties of the titanium.
  • the furnace arrangement and heating cycle will be such that during the heating step the titanium is always surrounded by a protective atmosphere containing the fluoride salt so that it is protected from reaction with oxygen, nitrogen, carbon, hydrogen or the like.
  • a method of making a titanium compound selected from titanium nitride, titanium carbide, titanium boride, titanium hydride, titanium silicide, titanium phosphide and titanium sulphide including the step of
  • the source of nitrogen, carbon, hydrogen, silicon or sulphur may be the corresponding elements, for example nitrogen and hydrogen as the gas, carbon as powder or coke, silicon as powdered silicon and sulphur as powdered sulphur.
  • the source of boron may be diborane.
  • the source of phosphorous may be phosphine.
  • the titanium nitride may have an x-ray diffraction pattern as set out in FIG. 12 .
  • the (M I )aXb was preferably added in the form of the dry salt.
  • M II TiF 6 .6H 2 O in which M II is Fe 2+ Mn 2+ , Zn 2+ , Mg 2+ , Cu 2+ or the like
  • M I Cl in which M I is Li + , Na + , K + or NH 4 +
  • the M I 2 TiF 6 intermediate precipitates almost quantitively from the solution while the M II Cl 2 , which is co-produced in the reaction, remains in solution.
  • Chloride was used in preference to SO 4 2 ⁇ because of its higher solubility and easier recycling loops.
  • Other anions like CH 3 COO ⁇ , NO 2 ⁇ , and the like can also be used for selective precipitation but NO 3 ⁇ is not suitable because it causes oxidation of Fe 2+ or Mn 2+ .
  • the first approach involves the reduction of Na 2 TiF 6 or K 2 TiF 6 produced from the (NH 4 ) 2 TiF 6 .
  • Na 2 TiF 6 can be precipitated from a saturated solution of (NH 4 ) 2 TiF 6 by the addition of sodium chloride.
  • the NH 4 Cl produced as a byproduct can then be filtered from the precipitate and crystallised for re-use in the selective precipitation step.
  • the Na 2 TiF 6 (mp. 700° C.) can be reduced under an argon atmosphere. Reduction is exothermic at the melting point of the salt. Sodium or magnesium (10% stoichometric excess) is usually used as the reducing agent but potassium or calcium can also be used.
  • the fluoride-titanium mixture is then fed into a vertically arranged elongate tubular zirconia or molybdenum crucible under an argon atmosphere.
  • the top of the crucible is heated to 1300° C. and the bottom to 1700° C.
  • the bulk of the molten 6NaF (mp. 990° C.) or 2NaMgF 3 (mp. 1030° C.) is tapped from the crucible above the molten titanium and the remainder of the molten fluoride acts as a blanket on top of the molten titanium (mp 1670° C.) to protect it from oxygen and nitrogen.
  • the molten titanium is then cast into ingots or other products in a molten fluoride eutectic consisting, for example, of 40 mole % NaF and 60 mole % LiF (mp. 652° C.), to allow for the titanium to anneal at 700° C. In this way the titanium is still protected against oxidation and nitrification during the annealing process.
  • the second approach to the production of titanium involves the pre-reduction of (NH 4 ) 2 TiF 6 to a Ti 3+ species, conversion of the Ti 3+ species to TiF 3 and reduction of the TiF 3 to titanium metal.
  • the (NH 4 ) 2 TiF 6 produced in the selective precipitation step can be reduced with Al (Hg-activated) or with Mn without the addition of an acid.
  • Typical products of the reduction are NH 4 TiF 4 and (NH 4 ) 3 AlF 6 or (NH 4 ) 2 TiF 5 and MnF 2 .
  • the (NH 4 ) 3 AlF 6 is more soluble and can be removed from the almost insoluble NH 4 TiF 4 precipitate by acid filtration. The latter can then be decomposed at 700° C. to produce NH 4 F (g) and TiF 3 (s).
  • Na 3 AlF 6 (cryolite) can be precipitated as a by-product with NaCl and the resulting ammonium salt can be recycled.
  • a typical product is (NH 4 ) 2 HTiF 6 which is freely soluble in acid (pH 1-2) while the reducing agent-fluorides are much less soluble and can be separated from the (NH 4 ) 2 HTiF 6 by filtration. Raising the pH with NH 4 OH (pH 6) precipitates (NH 4 ) 3 TiF 6 . After filtration and drying, the product can be decomposed at 700° C. to produce 3NH 4 F(g) and TiF 3 (s).
  • an alternative option is to reduce (NH 4 ) 2 TiF 6 electrolytically.
  • a membrane such as a canvas membrane is used to separate the anode from the cathode. Normally a lead anode and a graphite cathode are used.
  • the anode side is filled with 0.1 N HF solution and the cathode side is filled with a saturated (NH 4 ) 2 TiF 6 solution, acidified with HF to pH 1.
  • the pH of the violet (NH 4 ) 2 HTiF 6 solution is increased by addition of NH 4 OH to pH 6 to precipitate (NH 4 ) 3 TiF 6 .
  • the product can be decomposed at 700° C. to produce 3NH 4 F (g) and TiF 3 (s). The Ti 3+ is then reduced to titanium metal.
  • TiF 3 can be reduced with Na, Mg or Al to produce 3NaF(Ti), 11 ⁇ 2MgF 2 (Ti) or AlF 3 (Ti) respectively.
  • the reduction of TiF 3 is less exothermic than the reduction of (Na,K) 2 TiF 6 and occurs above 700° C.
  • the NaF or MgF 2 can be melted from the titanium while AlF 3 will sublime at 1300° C.
  • a 30 ⁇ 10% excess ilmenite is maintained during digestion. Because of its coarseness and high density, the excess ilmenite settles out from the leachate and the light insoluble precipitate after digestion.
  • the digested suspension is pumped off from the settled ilmenite and filtered.
  • the filter cake is then re-slurried and screened through a 45 ⁇ m screen.
  • the top fraction (ilmenite) is recycled back into the digestion tank while the bottom fraction (mostly acid insolubles) is waste. In this way a digestion efficiency of greater than 90% is achieved.
  • the choice of the reducing agent determines the choice of the salt used for the selective precipitation. Sodium favours a chloride precipitate while magnesium favours a sulphate precipitate.
  • the recycling loops are set out in FIGS. 16 and 17 which respectively show the production of high purity titanium and of grade 4 titanium.
  • the recycling loops will be essentially the same as those for the Option A process as indicated in FIG. 1 .
  • the fluoride salts of the reducing agents would be by-products.
  • Fe 2 O 3 is the major by-product of the process of the invention. If magnesium is used as the reducing agent and not regenerated, Mg(OH) 2 or MgSO 4 will also be by-products.
  • FIG. 1 is a general flow diagram of the invention
  • FIG. 2 is a flow diagram for the preferred route
  • FIG. 3 is an x-ray diffraction pattern of selectively precipitated (NH 4 ) 2 TiF 6 ;
  • FIG. 4 is an x-ray diffraction pattern of the (NH 4 ) 2 TiF 6 of FIG. 3 after recrystallisation;
  • FIG. 5 is an x-ray diffraction pattern of NH 4 TiF 4 produced by the reduction of (NH 4 ) 2 TiF 6 with Al(Hg);
  • FIG. 6 is an x-ray diffraction pattern of TiF 3 produced by the decomposition of the NH 4 TiF 4 of FIG. 5 ;
  • FIG. 7 shows superimposed x-ray diffraction patterns of standard samples of TiF 3 and FeF 3 ;
  • FIG. 8 is an x-ray diffraction pattern of the reduction product of TiF 3 with aluminium at 750° C.
  • FIG. 9 is an x-ray diffraction pattern of AlF 3 sublimed at 1250° C.
  • FIG. 10 is an x-ray diffraction pattern of the product of FIG. 8 after sublimation of AlF 3 ;
  • FIG. 11 is an x-ray diffraction pattern of titanium metal produced from the powder of FIG. 10 ;
  • FIG. 12 is an x-ray diffraction pattern of titanium nitride formed by exposing the titanium powder of FIG. 10 to nitrogen at 1350° C.;
  • FIG. 13 is an x-ray diffraction pattern of NH 4 VF 4 produced by the reduction of (NH 4 ) 2 VF 6 with Al(Hg);
  • FIG. 14 is an x-ray diffraction pattern of VF 3 produced by the decomposition of the NH 4 VF 4 shown in FIG. 13 ;
  • FIG. 15 shows the titanium powder of FIG. 10 after soft sintering at 1250° C.
  • FIG. 16 is a flow diagram of the sodium reduction route
  • FIG. 17 is a flow diagram of the magnesium reduction route
  • Table 1 shows the chemical composition, mechanical properties and physical properties of different grades of titanium.
  • the process of the invention can be divided into five stages. These are the digestion of ilmenite, the selective precipitation of the titanium precursor produced in the digestion step, the reduction of the precursor, the melting of the reduced titanium product into an ingot and the recycling of the reagents used in the process.
  • Step 1 Digestion of Ilmenite with Dilute HF
  • Ilmenite concentrate was used as the feed material for the digestion step.
  • the material contained about 89.5% ilmenite, 6% hematite, 2.5% quartz and 2% other metal oxides.
  • the particle size was uniform and approximately 98% of the material had a particle size of between +45 ⁇ m and ⁇ 106 ⁇ m.
  • the material typically had the following chemical composition:
  • the ilmenite used consisted of FeTiO 3 (89.5%), Fe 2 O 3 (6.0%), SiO 2 (2.5%) and other material (2%). This corresponded to FeTiO 3 (447.5 g; 2.95 mol), Fe 2 O 3 (30 g; 0.19 mol) and SiO 2 (12.5 g; 0.21 mol) in 500 g.
  • the FeTiO 3 , Fe 2 O 3 and SiO 2 each require 6 mol of HF per mole for conversion, respectively, to FeTiF 6 , FeF 3 and H 2 SiF 6 .
  • the suspension was then filtered and washed with tap water (2 ⁇ 50 ml). Approximately 200 g of moist filter cake was obtained. This material was re-slurried to recover most of the excess ilmenite and a leachate of 1375 ml containing FeTiF 6 was obtained.
  • the Ti concentration in the leachate was approximately 100 g/t implying a Ti recovery of 137.5 g.
  • the recovery efficiency was calculated as follows:
  • the resulting crystalline (NH 4 ) 2 TiF 6 was filtered at 15-20° C., and pressed inside the filter head to remove as much excess liquid as possible. The vacuum was then broken and ice water (184 ml; 5° C.) was added to the product. The vacuum could be restored only after the water had penetrated the filter cake (approximately 2 minutes later) and the crystalline (NH 4 ) 2 TiF 6 had the appearance of icing-sugar. The crystalline product was sucked and pressed as dry as possible.
  • the vessel was cooled to about 40° C. with cold water, and ice and cold water were then used to cool the vessel to 10° C. while stirring the resulting crystalline (NH 4 ) 2 TiF 6 .
  • the crystalline product was filtered and pressed inside the filter head to remove as much excess liquid as possible.
  • the vacuum was then broken and ice water (50 ml; 5° C.) was added to the crystalline product.
  • the vacuum could be restored only after the water had penetrated the filter cake (approximately 2 minutes later) and the crystalline product had the appearance of icing-sugar.
  • the crystalline product was then sucked and pressed as dry as possible.
  • the resulting crystalline (NH 4 ) 2 TiF 6 was dried at 60° C. The yield was typically about 70% of the feed crystalline product without evaporation of additional water. The XRD of this product is shown in FIG. 4 .
  • Step 3 Reduction of (NH 4 ) 2 TiF 6 with Al(Hg)
  • buttons (ID approximately 10-15 mm, 1-3 mm thick, 150 g) were covered with a 1N NaOH solution in a 500 ml plastic beaker and Hg (approximately 50 ml) was added. The buttons were mixed using a plastic stirrer and dipped into the Hg. After about 5 minutes, the buttons were completely coated with Hg.
  • the sodium hydroxide was removed by rinsing the buttons with a strong flow of tap water inside the beaker for about 1 minute.
  • the Al(Hg)-buttons were screened (500 ⁇ m) from the acetone and free Hg, and immediately dropped into the (NH 4 ) 2 TiF 6 solution as described below.
  • the Al(Hg)-buttons (150 g) prepared as described above were added to the (NH 4 ) 2 TiF 6 solution, while stirring (no vortex). The reaction was exothermic and the temperature rose from 30 to 70° C. over a period of 75 minutes. After 15 minutes at 70° C., the suspension was cooled to below 30° C. and filtered.
  • the Al(Hg)-buttons were rinsed with water and stored in acetone.
  • the violet precipitate was filtered and sucked as dry as possible and washed with water (2 ⁇ 50 ml).
  • the violet precipitate was dried at 60° C. (yield 475 g).
  • the product consisted of NH 4 TiF 4 and (NH 4 ) 3 AlF 6 in a weight ratio of approx 75%:25%.
  • NH 4 TiF 4 has a low solubility in dilute HF and an even lower solubility in concentrated HF. In this way, if necessary, the (NH 4 ) 3 AlF 6 (and other impurities) could be washed out of the product.
  • the XRD of this clean product is shown in FIG. 5 .
  • Step 4 Decomposition of NH 4 TiF 4 and (NH 4 ) 3 AlF 6
  • step 3 consisting of a mixture of NH 4 TiF 4 and (NH 4 ) 3 AlF 6 , was decomposed at 600° C. under a nitrogen or argon atmosphere in a mild steel rotary. After 2-4 hours of soaking, the light brown-maroon product, consisting of TiF 3 and AlF 3 , was completely free of NH 4 F which had evaporated. The evaporated material was condensed and collected. It was found that, if traces of NH 4 F remained, TiN formed during the reduction with Al at 750° C.
  • the yield of the decomposed product was typically between 60 and 70% of the feed.
  • NH 4 TiF 4 is a hitherto unknown salt and there is accordingly no data with which to compare the XRD powder pattern of NH 4 TiF 4 as shown in FIG. 5 .
  • the closest XRD fit to this salt is the XRD of NH 4 FeF 4 . It is therefore not unexpected that the decomposed product, TiF 3 of NH 4 TiF 4 best matches the XRD powder pattern of FeF 3 .
  • the XRD powder patterns of standard samples of FeF 3 and TiF 3 are shown in FIG. 7 .
  • Step 5 Reduction of TiF 3 with Al and Sublimation of AlF 3
  • Al-powder ( ⁇ 125 ⁇ m) was mixed with the product. A stoichiometric amount of Al to TiF 3 , was used (1 mol:1 mol). The mixture was placed in a mild steel crucible under an argon atmosphere and heated to 750° C. After 2 hours of soaking, the reduction was complete without any change in mass. The XRD of this material is shown in FIG. 8 .
  • the coarsest Al powder that could be used was ⁇ 125 ⁇ m. It is expected that, in a rotary unit, liquid Al may completely wet the TiF 3 and thus complete the reduction. Alternatively, the Al may be dissolved in Zn to increase the surface area of the Al to complete the reduction. After reduction, the Zn could be evaporated at 950° C., condensed and re-used in the next run.
  • Step 6 Melting of Ti-Powder
  • the Ti-powder produced in step (5) was pressed inside a zirconia lined clay crucible and melted in an induction furnace under an argon atmosphere. It readily melted to form a small ingot and a trace amount of AlF 3 in the form of fumes was produced.
  • the XRD of the metal is shown in FIG. 11 .
  • the Ti-powder or metal produced in this way contained very low levels ( ⁇ Ti-grade 1) of oxygen, nitrogen, carbon and hydrogen due to the fluoride protection described above.
  • the process of the invention allows Ti to be produced by reduction with Al without the formation of Al—Ti alloys.
  • the XRDs of the Ti-powder after reduction as shown in FIG. 8 and after sublimation as shown in FIG. 10 appear to reveal the presence of the AlTi 3 phase (instead of Ti phases only), the Applicant believes that the AlTi 3 phase which is apparently shown in the XRDs is only a pseudo AlTi 3 phase and that there is, in fact, no Al present.
  • Ti 3 has the AlTi 3 crystal structure because it was “born” from Al and, at the low temperature used ( ⁇ 1300° C.), there is not enough energy to re-arrange the titanium crystal structure. Rearrangement of the titanium crystal structure only takes place when the Ti is melted or reacted with something else, such as N 2 , to form TiN.
  • FIG. 12 shows the XRD where the Ti-powder was exposed to a limited amount of N 2 at 1350° C. As can be seen no Al or Al alloy phase was detected.
  • Ti can be reduced by Al without alloying.
  • Al reacts with Ti(III) and not Ti(IV).
  • the former reaction is moderately exothermic while the latter reaction is violently exothermic:
  • Alloying occurs when two metals are in contact with one another and there is enough energy to form an alloy.
  • Step 1 Preparation of NH 4 VF 4 and VF 3
  • Ti-alloys such as Ti-6Al-4V
  • the alloying elements in the form of their metal fluorides were mixed in the correct ratio with TiF 3 prior to reduction with Al.
  • VF 3 was added to TiF 3 and 6% excess Al was used during the reduction to produce the alloy-powder, after sublimation of AlF 3 .
  • V could not be introduced as VF 5 or VF 4 due to the low boiling points of these compounds since they would sublime before reduction could take place. It was therefore necessary to produce VF 3 as the V precursor as set out below.
  • the temperature of the blue solution was adjusted to 20° C. and then reduced with Al(Hg)-buttons. Over a period of approx 3 hours, the temperature increased to about 40° C. When the reduction of V(IV) to V(III) had completed, Fe plated onto the Al(Hg)-buttons and the reduction stopped.
  • the pH of 1 liter of the (NH 4 ) 2 FeCl 4 solution produced in the selective precipitation step was increased to 4-5 by addition of NH 4 OH while stirring.
  • the solution/suspension was stirred, it was electrolysed using a car battery charger at a voltage of 6V and 2 graphite electrodes (any suitable electrodes can be used). A current of 6-9 amps was produced. This current also heated the solution to 60-70° C., which aided the reaction.
  • Plated Fe was recovered from the cathode and a brown-orange precipitate was readily filtered off. After drying at 80° C., 200 g of a product consisting mostly of FeO(OH) and some TiOF 2 and other impurities was obtained.
  • the plated Fe could be used in the process when iron reduction was carried out after digestion and to produce FeTi if needed.
  • NH 4 OH was used in the regeneration of NH 4 Cl from (NH 4 ) 2 FeCl 4 .
  • the CaF 2 (fluorspar) produced can be sold as a by-product or treated with concentrated H 2 SO 4 according to conventional processes to produce HF.
  • Crude anatase pulp (TiO 2 .xH 2 O) is a well-known product obtained by the aqueous hydrolysis of a Ti-solution. Essentially, all Ti feedstock materials can be converted to crude anatase pulp. To produce a concentrated solution of M II TiF 6 , it was necessary to add M II to obtain a mole ratio close to 1 mol M II :1 mol Ti IV . In this example M II was Zn 2+ .
  • the resulting leachate (1.5 l) contained 164 g of dissolved titanium.
  • Solid NH 4 Cl 49.4 g; 5% excess was added to the leachate (876 ml) and the temperature dropped to about 10° C.
  • the resulting solution was stirred for 1 hour in a water bath at 20° C.
  • Filtration produced (NH 4 ) 2 TiF 6 (454 g) as a moist white crystalline product containing 68 g water (equal to a dry weight of 386 g).
  • the theoretical yield is 395.8 g for 2 moles of (NH 4 ) 2 TiF 6 .
  • the selective precipitation accordingly has an efficiency of 97.5% and produces a product with a purity of about 98%.
  • the moist filter cake was then washed with a minimum amount of a saturated NH 4 Cl solution (approximately 75 ml), to yield a moist crystalline product (442 g).
  • This product contained about 66 g of water (equal to a dry weight of 376 g). indicating an efficiency of 95% and a purity of about 99%.
  • This product was added to sodium metal (115 g; 20% excess) in a 750 ml stainless steel crucible fitted with a loose lid under an argon atmosphere.
  • the crucible was placed in a muffle furnace (still under argon) and heated to about 700° C. At this temperature an exothermic reaction took place and the temperature spontaneously rose to about 900° C.
  • the crucible was kept at about 900° C. for a further 30 minutes to ensure that all of the excess sodium had evaporated, and then allowed to cool.
  • NaF 42 g; ⁇ 500 um
  • concentrated HCl 100 ml; 32%) solution were added to a 250 ml beaker with a loose lid and stirred at room temperature for 2 hours to produce an aqueous HF solution.
  • Fine crystalline NaCl 57 g after drying at 120° C.; >98%) was filtered from the solution (96 ml).
  • the HF was evaporated to a volume of 84 ml to obtain a 20% HF solution (indicating an efficiency of about 95%).
  • HCl and NaOH were recovered by electrolysis of a saturated NaCl solution. This is a well known industrial process and is used for example at the Chloorkop installation in South Africa on a kiloton scale.
  • Sodium silicate was recovered from sodium hydroxide and silica as is well known in, for example, the glass industry, and the sodium silicate was converted to sodium via Si(Fe) according to known methods.
  • Ilmenite 800 g was digested, with 20% aqueous HF to produce a leachate as described in Example 1.
  • Sodium sulphate 149 g; 5% excess was added to the leachate (438 ml) and the solution was stirred for 1 hour at 20° C.
  • the resulting suspension was filtered to produce a moist, white crystalline product which was washed with a minimum amount of a saturated Na 2 SO 4 solution (approximately 3 ⁇ 25 ml) and dried at 60° C., to give a crystalline Na 2 TiF 6 product (195 g; indicating an efficiency of 94% and a purity of about 99%).
  • the dried crystalline Na 2 TiF 6 product (195 g) was added to magnesium filings (57 g; 20% excess) in a 750 ml stainless steel crucible with a loose lid under an argon atmosphere.
  • the crucible was placed in a muffle furnace (still under argon) and heated to about 700° C. At this temperature an exothermic reaction took place and the temperature spontaneously rose to about 900° C. The temperature was then raised to about 1100° C. and kept at this temperature for about 30 minutes to ensure that all of the excess magnesium evaporated, and then allowed to cool.
  • the argon flow was stopped and the product consisting of a mixture of NaMgF 3 and titanium was recovered from the crucible. Because of the iron content of the precursor, only Ti-grade 4 was obtained by melting the product at 1700° C.
  • the recycling loops shown in FIG. 17 are well known commercial processes.
  • the deactivated titanium powder of Example 1 was heated in the presence, respectively, of gaseous nitrogen, carbon in the form of carbon powder or coke, diborane, gaseous hydrogen, powdered silicon, phosphine and powdered sulphur to produce titanium nitride, carbide, boride, hydride, silicide, phosphide and sulphide respectively.
  • Table 1 shows for comparison purposes the typical chemical composition, mechanical properties and physical properties of commercially available corrosion-resistant titanium alloys.
  • the Applicant has found that a very pure titanium precursor can be produced in high yield from ilmenite (which is the cheapest source of titanium) and that this precursor can be used to produce titanium metal with oxygen levels which are lower than those of commercial grade 1 titanium.
  • the low oxygen content increases the malleability of the metal.
  • the metal is also protected from oxidation during forging via a metal fluoride based coating.
  • the Applicant believes that the method of the invention will allow titanium to be produced at a cost which is approximately the same as that of high-grade stainless steel. This would greatly increase the world market for titanium.

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US20100173170A1 (en) * 2005-01-27 2010-07-08 Peruke Investment Holdings (Proprietary) Limited Method of Producing Titanium
US7846232B2 (en) * 2005-01-27 2010-12-07 Adams & Adams Method of producing titanium
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